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    • 专利摘要:
    Microcapsule composition, the microcapsules comprising (A) at least one leuco dye electron donor compound, (B) at least one electron acceptor compound, (C) a mixture comprising at least one 4-benzyloxyphenylalkyl ester compound and at least one glycerol triester compound. Cosmetic or dermatological or tattoo compositions comprising these microcapsules. Use for make-up, especially make-up of dander and for tattooing.
    公开号:FR3037236A1
    申请号:FR1555413
    申请日:2015-06-12
    公开日:2016-12-16
    发明作者:De Blanzy Benjamin Dapres；Nicolas Thiebault；Dominique Ribola；Yves Ortais
    申请人:Ink And Out Sas；
    IPC主号:
    专利说明:

    [0001] The present invention relates to a composition of microcapsules, the microcapsules comprising (A) at least one electron-donor leuco dye compound, (B) at least one acceptor compound of at least one electron-donating compound, and electrons, (C) an ester mixture comprising at least one 4-benzyloxyphenylalkyl ester compound and at least one glycerol triester compound. It also relates to the cosmetic or dermatological compositions comprising these microcapsules and the use of this composition for makeup, in particular the makeup of integuments (nails, hair, eyelashes), and in particular a nail polish composition. It also relates to tattoo compositions comprising these microcapsules. Finally, it relates to a makeup process and a tattooing method which comprises applying the composition comprising the microcapsules and the application of temperature changes.
    [0002] STATE OF THE PRIOR ART Various prior art thermochromic compositions, and in particular makeup compositions having the capacity to change color as a function of temperature, are known from the prior art. Several documents mention the use of thermochromic pigments in makeup compositions, especially nail polish compositions, but do not specify the nature of the pigment compositions used. WO93 / 18098 discloses thermochromic varnish compositions, the pigment consisting essentially of an electron donating chromogenic material, a 1,2,3-triazole compound, a weakly basic, slightly soluble azomethine or a sodium salt. primary amine and carboxylic acid and an alcohol, amide or ester as a solvent. The thermochromic pigment compositions described in this document have a color change temperature of around 30 ° C, with a small hysteresis width and thus a limited color memory. The color change seems almost continuous. There is no mention of complete discoloration. EP2412762 discloses a thermosensitive ink composition formulated with dyes comprising a leuco dye, a developer and a crystalline substance such as a fatty acid, an amide or a fatty ester. These systems are implemented without microcapsule and do not recolor, even after application of a temperature below -50 ° C. U82010 / 0310300 describes thermochromic compositions intended essentially for application in inks. These compositions are based on microcapsules comprising at least one electron-donor leuco dye compound, at least one 4-benzyloxyphenylethyl ester. These compositions have a high hysteresis width, a high fading temperature, which is not compatible with a cosmetic application, particularly an application to the nails. Compositions having the lowest fading temperatures (about 55 ° C) have very low color temperatures (below -20 ° C) which are also not compatible with cosmetic application. EP708153 discloses thermochromic microencapsulated pigment compositions obtained from esters of aliphatic alcohols having an odd number of carbon atoms. These pigments have a wide hysteresis, from 8 to 30 ° C. However, the examples illustrate ranges of coloring temperature / discoloration unsuitable for use in cosmetics. In particular, these pigments lack stability over a wide range of temperatures around the ambient temperature to allow such use.
    [0003] In the field of tattooing the ability to color / bleach a tattoo on demand simply by applying a temperature change is particularly interesting, because the wearing of tattoos may be unappreciated in some social-professional circles. The safety of such compositions is an important point for their use.
    [0004] Therefore, there remained the need for a thermochromic pigment composition for complete coloration and decolorization. There remained the need for a thermochromic pigment composition having a coloring temperature and a bleaching temperature compatible with cosmetic / dermatological use or tattooing, and a staining / fading memory effect over a sufficiently wide range, around Room temperature. In addition, an attempt has been made to develop a composition that is simple and non-toxic. SUMMARY OF THE INVENTION The invention relates to microcapsules comprising: (A) at least one electron donor leuco dye compound, (B) at least one electron acceptor compound, (C) a mixture comprising - at least one compound of formula (I) in which R1 represents a C5-C23 alkyl or alkenyl group, n represents an integer ranging from 1 to 6, and - at least one compound of formula (II) o R2 Wherein R2 represents a C5-C23 alkyl or alkenyl group. According to a preferred embodiment, the compound of formula (II) is glycerol trilaurate and the compound of formula (I) is 4-benzyloxyphenylethyl laurate. According to a preferred embodiment, the mass ratio of the compounds (II) / (I) in the mixture (C) ranges from 10/1 to 1/4, preferably from 5/1 to 1/2, more preferably from 3 to / 1 to 1/1. According to a preferred embodiment, the microcapsules have a fading temperature in a range from 32 to 55 ° C., preferably from 35 to 50 ° C., and a restoring temperature in a range from 2 to 20 ° C., preferentially from 5 to 15 ° C. The subject of the invention is also a cosmetic or dermatological composition comprising microcapsules according to the invention in a cosmetically or dermatologically acceptable support.
    [0005] According to a preferred embodiment of the cosmetic or dermatological composition, the support is adapted to the makeup of the integuments, preferably the composition is a nail polish composition. The invention also relates to a tattoo composition comprising microcapsules according to the invention in a support adapted for subcutaneous injection.
    [0006] Another subject of the invention is a makeup or tattooing method which comprises: the application to the skin or integuments, preferentially the nails, of a make-up composition according to the invention; invention, or the subcutaneous injection of a tattoo composition according to the invention, and - the application to make-up or tattooing of a temperature ranging from: 32 to 55 ° C, preferably from 35 to 50 ° C, ie 2 to 20 ° C, preferably 5 to 15 ° C.
    [0007] According to a preferred embodiment, the makeup or tattooing method comprises: the application to the skin or integuments, preferentially the nails, of a make-up composition, or the subcutaneous injection of a tattoo composition, and - the application to make-up or tattooing of at least one heat treatment cycle to at least a portion of the make-up or tattoo, resulting in the discoloration and the recolouration or the change in the color of the make-up or the tattoo. 20 tattoo. The invention further relates to the use of microcapsules comprising: (A) at least one electron donor leuco dye compound, (B) at least one electron acceptor compound, (C) a mixture comprising at least one compound of formula (I) R-1 (I) wherein R1 represents a C5-C23 alkyl or alkenyl group, n represents an integer from 1 to 6, and at least one compound of formula (II) ICG70047 Text in which R2 represents a C5-C23 alkyl or alkenyl group, for the manufacture of a thermochromic composition intended for a cosmetic or dermatological application or a tattooing application.
    [0008] The invention relates to pigment compositions in the form of microcapsules having temperature sensitivity and staining / fading memory properties. These compositions exhibit the property of being able to stain and discolor at temperatures compatible with cosmetic, dermatological or tattoo application and to exhibit staining / discoloration stability at room temperature over a wide temperature range. Thus, the user chooses a state of the microcapsule (colored / discolored) by conditioning at a certain temperature and this state persists after returning to ambient temperature and until the application of a change of state temperature. FIG. 1: FIG. 1 is a graph showing schematically the hysteresis characteristics of the thermochromic dye memory composition according to the invention in the form of color-temperature intensity curves. The operation of the microcapsules is described with reference to FIG. 1, in particular the relationship between the color intensity and the temperature, as well as the hysteresis characteristics on which the memory effect is based. In FIG. 1, the color intensity is on the ordinate and the temperature on the abscissa. The arrows indicate variations in color intensity. Point A indicates the staining intensity at a temperature T4, the lowest temperature that can cause a completely discolored state (hereinafter referred to as the staining / fading threshold temperature). Advantageously, in the microcapsule compositions of the invention, this temperature T4 is of a value which can range from 40 to 55 ° C., preferably from 43 to 50 ° C. Point B indicates the staining intensity at a temperature T3, the highest temperature at which a fully colored state can be maintained (hereinafter referred to as the highest temperature of color retention). In the microcapsule compositions of the invention this temperature T3 is about 34 to 45 ° C. The invention is particularly notable in that in the microcapsule compositions of the invention, the difference T4-T3 is less than or equal to 10 ° C. Thus, the color remains intense up to a T3 value very close to T4 and then disappears very quickly by conditioning at a suitable temperature. Point C indicates the staining intensity at a temperature T2, the lowest temperature at which a fully discolored state can be maintained (hereinafter referred to as the lowest temperature for maintaining discoloration). In the microcapsule compositions of the invention this temperature T2 is about 10 to 20 ° C. Dot D indicates the staining intensity at a temperature T1, the highest temperature that can cause a completely colored state (hereinafter referred to as the complete staining temperature). In the microcapsule compositions of the invention, this temperature T1 is of a value which can range from 2 to 15 ° C, preferably from 5 to 15 ° C. The invention is particularly notable in that in the microcapsule compositions of the invention, the T2-T1 difference is less than or equal to 5 ° C, preferably T2-T1 is less than or equal to 3 ° C. Thus, the discoloration persists until a T1 value very close to T2 then the color appears very quickly by conditioning at a suitable temperature. At an intermediate temperature between T4 and T1, which is compatible with both states, one can have colored or discolored microcapsules depending on the history of the thermal conditioning of the microcapsules. In the corresponding temperature zone, which is compatible with both states, the state obtained by heat treatment: colored or bleached, can be maintained. The invention is particularly remarkable in that, in the microcapsule compositions of the invention, the difference T4-T1 is greater than or equal to 30 ° C.
    [0009] Thus, the selected state, colored or bleached, can be maintained over a wide range of temperatures. And the length of the T4-T1 segment corresponds to the hysteresis temperature range (hereinafter referred to as the hysteresis range AH). The larger the hysteresis range AH, the more easily the state obtained, colored or bleached, can be maintained. The microcapsules components: The invention relates to microcapsules comprising: (A) at least one electron donor leuco dye compound, (B) at least one electron acceptor compound, (C) a mixture of comprising - at least one compound of formula (I) wherein R1 represents a C5-C23 alkyl or alkenyl group, n represents an integer ranging from 1 to 6, and - at least one compound of formula (I) II) wherein R2 represents a C5-C23 alkyl or alkenyl group.
    [0010] In these thermochromic compositions, the components (A), (B) and (C) make it possible to act respectively on the type of shade, the color density and the coloring and fading temperature. By combining these components, various reversible thermochromic compositions can be obtained depending on the relative proportions of the components of the composition, these relative proportions making it possible to determine the type of shade, the color density, the fading temperature and the temperature range. of conservation of the chosen state. The electron donor leuco dye compound (A): The choice of the electron donor dye compound (s) determines the hue of the microcapsule.
    [0011] In a known manner, the compound (A) may be chosen in particular from: spirolactones such as fluoranes and crystal violet lactone, (aza) phthalides such as arylmethane (aza) phthalides and (phenyl) indolyl (aza) phthalides, spirogens, lactams such as rhodaminelactams, di- and tri-arylmethanes such as diphenylmethanes, fulgides, chromenes, styrylquinolines, diazarhodamine lactones and mixtures thereof. Specific examples of leuco dyes include: 3,3-bis (p-dimethylaminophenyl) -6-dimethylaminophthalide, 3,3-bis (p-dimethylaminophenyl) phthalide, 3- (p-dimethylaminophenyl) -3- (1,2-dimethylindol-3-yl) phthalide, dimethylaminophenyl) 3- (2-methylindol-3-yl) phthalide, 3,3-bis (1,2-dimethylindol-3-yl) -5- dimethylaminophthalide, 3,3-bis (1,2-dimethylindol-3-yl) -6-dimethylaminophthalide, 3,3-bis (9-ethylcarbazol-3-yl) -6-dimethylaminophthalide, 3.3 (2-phenylindol-3-yl) -6-dimethylaminophthalide, 3-p-dimethylaminophenyl-3- (1-methylpyrrol-3-yl) -6-dimethylaminophthalide, 4,4'-bisdimethylaminobenzhydryl benzyl ether, N-halophenyleucoauramine, N-2,4,5-trichlorophenyl-leucoauramine, rhodamine-B-anilinolactam, rhodamine- (pnitroanilino) lactam, rhodamine- (o-chloroanilino) lactam, 3-dimethylamino-7- Methoxyfluorane, 3-diethylamino-6-methoxyfluorane, 3-di-ethylamino-7-methoxyfluoro ran, 3-diethylamino-7-chlorofluorane, 3-diethylamino-6-methyl-7-chlorofluorane, 3-di-ethylamino-6,7-dimethylfluorane, 3- (N-ethyl-p-toluidino) - 7-methylfluorane, 3-diethylamino-7- (N-acetyl-N-methylamino) fluorane, 3-diethylamino-7- (N-methylamino) fluorane, 3-diethylamino-7-dibenzylaminofluorane, 3- diethylamino-7- (N-methyl-N-benzylamino) fluoran, 3-diethylamino-7- (N-chloroethyl N -ethylamino) fluoran, 3-diethylamino-7-N-diethylaminofluorane, 3- (N-ethyl-p-toluidino) -6-methyl-7-phenylaminofluorane, 3- (N-ethyl-p-toluidino) -6-methyl-7- (p-toluidino) fluoran, 3-diethylamino-6 Methyl-7-phenylaminofluorane, 3-dibutylamino-6-methyl-7-phenylaminofluorane, 3-diethylamino-7- (2-carbomethoxyphenylamino) fluorane, 3- (N-cyclohexyl-N-methylamino) -6- methyl-7-phenylaminofluorane, 3-pyrrolidino-6-methyl-7-phenylaminofluorane, 3-piperidino-6-methyl-7-phenylaminofluorane, 3-diethylamino-6-m ethyl-7- (2,4-dimethylamino) fluoran, 3-diethylamino-7- (o-chlorophenylamino) fluoran, 3-dibutylamino-7- (o-chlorophenylamino) fluoran, 3-pyrrolidino- 6-methyl-7- (p-butylphenylamino) fluoran, 3- (N-methyl-N-amylamino) -6-methyl-7-phenylaminofluorane, 3- (N-ethyl-Nn-amylamino) -6-methyl 7-phenylaminofluorane, 3- (N-ethyl-N-isoamylamino) -6-methyl-7-phenylaminofluorane, 3 - (N-methyl-Nn-hexylamino) -6-methyl-7-phenylaminofluorane, 3 (N-ethyl-Nn-hexylamino) -6-methyl-7-phenylaminofluorane, and 3- (N-ethyl-N-3-ethylhexylamino) -6-methyl-7-phenylaminofluorane. Naturally, (A) may be a mixture of electron donor leuco dye compounds. The electron acceptor compound (B): The compound (B), which is the electron acceptor compound, can be selected from the group consisting of compounds having active proton (s), compounds pseudo-acids (which are not true acids but act as acids in the compositions by developing the color of the component (A)), compounds having one or more electron hole (s). The compounds having one or more active proton (s) are, for example: compounds having a monophenol and / or polyphenol group, that is to say compounds having one or more hydroxyl group (s) ) phenol (s), and optionally having a substituent (s) selected from alkyl, aryl, acyl, alkoxycarbonyl, carboxy, carboxylic, amide, halogen; phenols having two or three substituents, such as bis or tris phenols; phenol-aldehyde condensation resins; metal salts of the above compounds. Examples of the electron acceptor component (B) include: phenol, o-cresol, tert-butylcatechol, nonylphenol, n-octylphenol, ndodecylphenol, n-stearylphenol, p-chlorophenol, p-chlorophenol, p-chlorophenol bromophenol, ophénylphenol, p-hydroxy-n-butyl benzoate, p-hydroxy-n-octylbenzoate, resorcinol, dodecyl gallate, 2,2-bis (4'-hydroxyphenyl) propane, 4,4-dihydroxydiphenylsulfone, 1,1-bis (4'-hydroxyphenyl) ethane, 2,2-bis (4'-hydroxy-3-methylphenyl) propane, bis (4-hydroxyphenyl) sulfide, phenyl-1,1-bis (4'-hydroxyphenyl) ethane, 1,1-bis (4'-hydroxyphenyl) -3-methylbutane, 1,1-bis (4'-hydroxyphenyl) -2-methylpropane, 1,1-bis (4'-hydroxyphenyl) n-hexane, 1,1-bis (4'-hydroxyphenyl) n-heptane, 1,1-bis (4'-hydroxyphenyl) n-octane, 1,1-bis (4'-hydroxyphenyl) n-nonane, 1,1-bis (4'-hydroxyphenyl) n-decane, 1,1-bis (4'-hydroxyphenyl) n-dodecane, 2, 2-bis (4'-hydroxyphenyl) butane, ethyl 2,2-bis (4'-hydroxyphenyl) propionate, 2,2-bis (4'-hydroxyphenyl) -4-methylpentane, 2,2-bis (4'-hydroxyphenyl) hexafluoropropane, 2,2-bis (4'-hydroxyphenyl) n-heptane, 2,2-bis (4'-hydroxyphenyl) n-nonane. Component (B) may also be chosen from aromatic carboxylic acids, aliphatic carboxylic acids having 2 to 5 carbon atoms, metal salts of carboxylic acids, acid phosphates and metal salts thereof, 1, 2,3-triazole and their derivatives.
    [0012] In the case of an application in the form of a tattoo, or for any application where the compounds described above would not be desired, the compound (B) is advantageously chosen from: ICG70047 Deposition text 3037236 10 (i) mono acids or di-carboxylic acids having linear or branched, saturated or unsaturated, 12 to 24 carbon atoms, such as lauric acid, palmitic acid and stearic acid, (ii) mono-, di- or tri- alkyl esters of linear or branched, saturated or unsaturated C 1 -C 8 carboxylic acids and mono-, di or trivalent C 10 -C 24 alcohols, and said esters comprise at least one group selected from free -OH and -COOH groups, such as citric acid esters, adipic acid esters and esters of succinic acid, (iii) mono-, di- or tri-alkyl esters of linear or branched, saturated or unsaturated carboxylic acids, C10-C24, and linear or branched C 1 -C 8 mono-, di- or trivalent alcohols, and said esters comprise at least one group selected from -OH and -COOH, (iv) esters of hydroxybenzoic acids and of C10-C24 alcohols having from 1 to 3 hydroxy groups on the benzene ring, and mixtures thereof.
    [0013] According to a preferred embodiment of this variant, in particular for tattooing, the compound (B) is chosen from esters of hydroxybenzoic acid and C10-C24 alcohol, comprising from 1 to 3 hydroxyl groups on the benzene ring. preferably esters of gallic acid and of C10-C24 alcohols, such as, for example, dodecyl gallate.
    [0014] Of course (B) may be a mixture of electron acceptor compounds. The mixture (C) This mixture comprises: - at least one compound of formula (I) wherein R1 represents a linear or branched C5-C23 alkyl or alkenyl group, n represents an integer ranging from 1 to 6, and - at least one compound of formula (II) wherein R2 represents a linear or branched C5-C23 alkyl or alkenyl group. The choice of a mixture of the compounds (I) and (II) makes it possible to confer on the composition a wide hysteresis in a range of temperatures that makes it possible to use it in cosmetics, in particular in nail polish or tattooing compositions. In particular, the choice of this mixture makes it possible to obtain a fading temperature ranging from 40 ° C. to 50 ° C. and a restoring temperature ranging from 10 ° C. to 15 ° C.
    [0015] Preferably, the compound (I) is a 4-benzyloxyphenylethyl ester, ie a compound of formula (IA), in which R1 represents a linear or branched C5-C23: 11 5 R1 alkyl or alkenyl group ( IA) When R 1 and / or R 2 are alkenyl groups, they advantageously comprise one or two unsaturations. Preferentially, R1 and R2 represent alkyl groups. Advantageously, R1 and R2 are chosen from C9-C13 alkyl groups.
    [0016] Advantageously, R 1 and R 2 are chosen from linear alkyl groups. Preferentially, R1 and R2 represent the same group. Even more preferentially, R1 and R2 represent a linear C11 alkyl. Thus, according to this preferred embodiment, the compound of formula (II) is glycerol tri la laurate and the compound of formula (I) is 4-benzyloxyphenylethanol laurate. Advantageously, the mixture (C) comprises a mass ratio of the compounds (II) / (I) ranging from 10/1 to 1/4, preferably from 5/1 to 1/2, more preferably 3 / 1 to 1/1. Preferably, the mixture (C) is a mixture of glycerol tri-laurate / 4-benzyloxyphenylethanol laurate with a mass ratio ranging from 10/1 to 1/4, preferably from 5/1 to 1/2, even better from 3/1 to 1/1. The mixture may optionally comprise other compounds of esters, alcohols, carboxylic acids, ketones, amides or aromatic compounds, provided that the hysteresis characteristics are not modified. In this case, preferably the other components of the mixture (C) can represent up to 20% by weight with respect to the total weight of (C). Examples of such compounds include: saturated fatty acids such as decanoic acid, dodecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid, heptadecanoic acid, octadecanoic acid nonadecanoic acid, icosanoic acid, docosanoic acid, tetradocosanoic acid, hexadocosanoic acid, octadocosanoic acid; long chain alcohols such as caprylic alcohol, lauryl alcohol, myristic alcohol, cetyl alcohol, stearyl alcohol, behenyl alcohol, isostearyl alcohol, palmitoleic alcohol; the amides of the fatty acids described above, the esters of the fatty acids and alcohols described above, the esters of the fatty acids described above and polyols such as glycerol, propylene glycol, ethylene glycol; the ethers of the fatty alcohols described above; aromatic compounds such as diphenylpropanedione, dibenzyloxybenzene, diphenoxybenzene, diisopropylnaphthalene, benzylbiphenyl, benzylnaphthyl ether, dibenzyl sulfoxide, dimethylterephthalate, diphenylcarbonate, diphenylsulfone, fluoranthene, fluorene, methylhydroxynaphthalate, phenylhydroxynaphthalate, steranilide. The component (II) can be used in the mixture (C) in the form of a mixture which can comprise the glycerol mono, di and tri-ester and optionally glycerol. Advantageously, the components (I) and (II) represent at least 80% by weight of the total mass of the components of (C), advantageously at least 90% by weight, more preferably at least 95% by weight. According to a preferred variant, (C) is essentially composed of (I) and (II), more preferably (IA) and (II). Formulation of microcapsules: The components (A), (B) and (C) are advantageously present in the microcapsule formulation in the proportions corresponding to the following ranges: 1 part by weight of (A) from 0.1 to 50 parts by weight of (B), ICG70047 Text deposit 3037236 13 - from 1 to 800 parts by weight of (C). Preferably, the microcapsule formulation comprises: 1 part by weight of (A) from 0.5 to 20 parts by weight of (B), 5 to 200 parts by weight of (C). In addition to the components (A), (B) and (C), the formula may comprise conventional additives, provided that they do not degrade the coloring qualities of the microcapsules nor the hysteresis behavior. Examples and, but not limited to, antioxidants, ultraviolet light absorbers, infrared absorbents, dissolution assistants, preservatives. In addition, conventional non-thermochromic pigments or dyes may be added to the formulation. In this case, instead of a colored / faded state change, there is a change of color state (1) / color (2) of the formulation.
    [0017] Preferably, the components (A), (B) and (C) represent at least 80% by weight of the total weight of the formulation present in the microcapsule, advantageously at least 90% by weight, more preferably at least 95% by weight. mass. According to a preferred variant, the formulation present in the microcapsule is essentially composed of (A), (B) and (C).
    [0018] The components (A), (B) and (C) and optionally the other components are formulated in known manner as microcapsules. The formulation in microcapsules makes it possible to protect the mixture of (A), (B) and (C) from the other components of the cosmetic or tattoo formulation and to allow the thermochromic properties to be maintained over time. The advantage of microencapsulation is to maintain the chemical integrity of each thermochromic composition (eg (A) + (B) + (C)) and to protect it from the external environment. The products necessary to carry out microencapsulation must not react with the thermochromic composition. The size of the microcapsules depends on several factors such as the concentration and type of product used for microencapsulation. Microencapsulation is carried out by means of known techniques such as inter-facial polymerization, in-situ polymerization, liquid phase crosslinking coating, phase separation from an aqueous solution, phase separation from of organic solution, gaseous suspension coating, melt dispersion cooling, spray drying. The surface of the microcapsule can be coated with a resin layer so as to improve its stability and / or its surface properties. For example, interfacial polymerization of an isocyanate system, in situ polymerization of an epoxy resin or melamine can be carried out. The material of which the walls of the microcapsules are composed is advantageously chosen from: polyamides, polyesters, polyurethanes, urea-formaldehyde resins, epoxy resins, melamine-formaldehyde resins, polyethylene, polystyrene, polysiloxanes.
    [0019] Advantageously, the microcapsules have a mean diameter of between 0.5 and 50 [μm, preferably between 1 and 20 μm, more preferably between 5 and 15 μm. When the microcapsules are too large, their dispersion in the liquid phase leads to a system which lacks stability, and the coloration is not uniform. When the microcapsules are too small, it is difficult to obtain a high density staining, clearly visible to the naked eye. The microcapsules must be transparent or translucent, so as to allow the colored expression of their contents, and they must be stable up to at least 90 ° C. Cosmetic or dermatological formulation: The microcapsules of the invention can be used in any type of cosmetic or dermatological formulation such as for example: lipstick, foundation, powder, make-up pencil. Preferably, they are used in compositions intended for application to superficial body growths, which have a lower sensitivity to temperature compared to the skin. For example, there may be mentioned a hair spray composition, a mascara composition, a nail polish composition, false nails, a false nail nail coloring composition. The cosmetic support is chosen from known supports which are compatible with the use of the microcapsules of the invention. The cosmetic or dermatological composition may comprise several distinct microcapsules differing in color and / or hysteresis temperatures. Advantageously, the invention relates to the use of microcapsules in nail polish formulations. In known manner, a nail polish composition comprises a film-forming polymer, for example nitrocellulose, one or more resins, for example tosyl-formaldehyde resins, one or more plasticizers, for example camphor, rheology, such as stearalkonium hectorite, which acts as a thickener, anti-UV agents, solvents. The nail polish composition may also include one or more pigments, dyes, nacres. In this case, instead of a colored / faded state change, there is a change of color (1) / color (2) state of the composition. Cosmetic or dermatological composition may comprise any component usually known for the formulation of a cosmetic or dermatological support, since it does not degrade the microcapsules. There may be mentioned in particular: aqueous or organic solvents, especially alcoholic solvents, polymers, surfactants, fatty substances such as oils and waxes, thickening agents, preserving agents, fillers, dyes, pigments . Tattoo Formulation: Tattoo compositions usually include diluted pigments in a carrier. The tattoo carrier is generally ethanol, but may also include water, propylene glycol, glycerine. The tattoo composition may comprise several distinct microcapsules differing in color and / or hysteresis temperatures. The tattoo composition may also include one or more conventional tattoo pigments. In this case, instead of a colored / faded state change, there is a change of color (1) / color (2) state of the composition. Makeup method, tattooing method: The makeup composition is applied in known manner by means of any suitable applicator. For example, the nail polish composition is applied by means of a paintbrush. If it is a lacquer, it can be applied by spraying. For a mascara, it is deposited in a known manner by means of a brush. The tattoo composition is applied in known manner by means of adapted needles. It may be chosen to apply the makeup composition to all or part of the support in question, for example, the lacquer composition may be applied to part or all of the nails. The makeup or tattoo composition can be applied through a mask so as to define the contours of the precisely drawn area. After drying, the user of the make-up or tattoo composition 30 chooses the appearance that he wants to give to the composition: If he wishes to see the coloration present in the microcapsules, he submits the zone concerned to a cooling. In known manner, the cooling treatment may consist of soaking in chilled water, ventilation by a stream of cold air, massage by means of ice cubes. If it wishes not to see the coloration present in the microcapsules, it subjects the zone concerned to heating. In known manner, the heating treatment may consist of soaking in hot water, ventilation by a hot air stream, by means of a hair dryer, for example, ICG70047 Texte dépôt 3037236 16 or the application of a hot towel. The quality of the microcapsules of the invention makes it possible to obtain the desired state of coloration / discoloration in a few seconds of treatment. Then, as long as the makeup or tattooed areas are maintained at room temperature, over a temperature range of 15 to 35 ° C, and even from 10 to 40 ° C, the selected state is retained. When the user chooses to change the initial staining / fading state, he just has to apply a new treatment, which will also be preserved after returning to room temperature. It should be noted that the treatment may be applied to only part or the entire makeup or tattooed area. Thus, it is possible for the microcapsule composition to be in a colored state on a part of the surface made up or tattooed and discolored on another part of the surface made up or tattooed. The repetition of the coloring-fading cycles does not degrade the quality of the makeup or tattoo, the color retaining its intensity and hue. Experimental part: 15 Commercial raw materials: - Melamine formaldehyde resin: Cymel ® 385 marketed by Allnex - Glycerol trilaurate: Dynasan ® 114 sold by Sasol - Leuco dyestuff: Black XV marketed by Yamamoto Chemicals 20 Prepared raw materials in the laboratory: Protocol 1: Synthesis of 2- [4- (Benzyloxy) phenyl] ethyl dodecanoate To a solution of 2- (4-hydroxyphenyl) ethanol (5.0 g, 36.23 mmol) in anhydrous DMF (20 mL) is K2CO3 (15.0 g, 108.7 mmol) was added and the reaction mixture was stirred at room temperature for 30 minutes. Then benzyl bromide (6.24 g, 36.5 mmol) is added to the mixture and the reaction is stirred at room temperature for 4h. The reaction medium is neutralized with water (200 mL) and ethyl acetate (200 mL) is added. The organic phase is separated and the aqueous phase is extracted once more with ethyl acetate (100 mL). The organic phases are pooled and washed with water (3x100 mL), saturated NaCl solution (100 mL), and dried over sodium sulfate. The organic phase is filtered and evaporated under reduced pressure to yield 244- (Benzyloxy) phenyl] ethanol (white solid, 8g, 97%). To a solution of 2- [4- (Benzyloxy) phenyl] ethanol (25 g, 109 mmol) in pyridine (350 mL) was added dodecanoic acid chloride (38.8 mL). The medium is stirred at room temperature for 3 days. Then the medium is neutralized with water (10 mL) and then evaporated under reduced pressure. The residue is solubilized in cyclohexane (200 mL) and washed with water (3 × 200 mL). The ICG70047 organic deposit phase is recovered, dried over sodium sulfate and evaporated under reduced pressure to yield 2 [4- (benzyloxy) phenyl] ethyl dodecanoate (white solid, 44.7 g, 99%). Example 1: Protocol 2: Preparation of the composition of microcapsules of thermochromic pigment: Step 1: in a solution Si of 100 grams of water are dispersed 2 g of sodium alginate and 0.7 g of melamine formaldehyde resin. Step 2: A composition S2 is prepared by hot dissolving (70 ° C.) a mixture comprising: 2 g of Black XV leuco dye (component A), 10 g of bis-phenol A (component B) 26.4 g of benzyloxyphenylethyl 4-laurate and 53.6 g of glyceryl trilaurate (component C). Step 3: The solution S2 is poured without the Si solution with stirring (550 rpm) for two minutes, then 25 grams of a 25% solution of melamine formaldehyde in 75% water are poured slowly. The resulting emulsion is transferred with slow stirring at 700 rpm and kept in a water bath for 8 hours. After cooling the microcapsule suspension obtained, a discoloration temperature of 52 ° C. and a coloring temperature of 15 ° C. are observed.
    [0020] EXAMPLE 2 Protocol 2 according to Example 1 is applied using 2 g of Lactone crystal violet dye (component A) and 10 g of docecyl galate replacing bisphenol A (component B). Example 3 (Comparative): Protocol 2 according to Example 1 was used, using 80 g of glyceryl trilaurate instead of the mixture named component C. After cooling the suspension of microcapsules obtained, a temperature of early bleaching at 60 ° C and a recolouration temperature, in black of 0 ° C. Example 4 (Comparative): Protocol 2 according to Example 1 is applied using 80 g of benzyloxyphenylethyl 4-laurate instead of the mixture named component C. After cooling of the suspension of microcapsules obtained a fading start temperature of 30 ° C and a recolouration temperature of 5 ° C were observed. Example of Formulation 1: Nail Polish Composition A nail polish composition is prepared by mixing the following components. The quantities given are mass percentages.
    [0021] 10 Component Quantity Nitrocellulose 15% Resin Toluenesulfonamide formaldehyde 7% (Santolite MI-IP) ® Dibutylphthalate 5% Camphor 2.5% Stearalkonium hectorite 1.2% Benzophenone 0.2% Microcapsule composition (*) 1% Butyl acetate / Acetate of ethyl 50/50 Qsp 100 (*) obtained according to protocol 2, Example 1 The varnish composition is applied to the nails and left to dry. The coloring / discoloration is then observed at the expected temperatures of 15 ° C / 52 ° C by dipping the hand for a few moments in cold or hot water or by heating with a hair dryer. Example of Formulation 2: Tattoo Composition Microcapsule composition obtained according to Protocol 2, Example 2 is diluted in alcohol so as to allow subcutaneous injection. The tattoo composition is applied under the skin. The coloring / discoloration is then observed at the expected temperatures of 15 ° C / 52 ° C by immersing the hand for a few moments in cold or hot water or by heating with a hair dryer.
    [0022] 1CG70047 Deposit text
    权利要求:
    Claims (10)
    [0001]
    REVENDICATIONS1. Microcapsules comprising: (A) at least one electron donor leuco dye compound, (B) at least one electron acceptor compound, (C) a mixture comprising - at least one compound of formula (I) wherein R 1 in which R1 represents a C5-C23 alkyl or alkenyl group, n represents an integer ranging from 1 to 6, and - at least one compound of formula (II) in which R2 represents an alkyl group or C5-C23 alkenyl.
    [0002]
    2. Microcapsules according to claim 1, wherein the compound of formula (II) is glycerol tri-laurate and the compound of formula (I) is 4-benzyloxyphenylethyl laurate. 30
    [0003]
    3. Microcapsules according to any one of claims 1 and 2, wherein the mass ratio of the compounds (11) 1 (1) in the mixture (C) ranges from 10/1 to 1/4, preferably 5/1 at 1/2, even better from 3/1 to 1/1. 20 35 ICG70047 Filing text 3037236 20
    [0004]
    4. Microcapsules according to any one of claims 1 to 3, which have a fading temperature in a range from 32 to 55 ° C, preferably 35 to 50 ° C, and a temperature of recoloration in a range from 2 at 20 ° C, preferably 5 to 15 ° C.
    [0005]
    5. Cosmetic or dermatological composition comprising microcapsules according to any one of claims 1 to 4, in a cosmetically or dermatologically acceptable support.
    [0006]
    6. Cosmetic or dermatological composition according to claim 5, wherein the support is adapted to the makeup of the integuments, preferably the composition is a nail polish composition.
    [0007]
    7. A tattoo composition comprising microcapsules according to any one of claims 1 to 4, in a support adapted for subcutaneous injection.
    [0008]
    8. Makeup or tattooing process which comprises: - the application on the skin or integuments, preferably the nails, of a makeup composition according to any one of claims 5 and 6, or the subcutaneous injection a tattoo composition according to claim 7, and - the application to makeup or tattooing a temperature ranging from: 32 to 55 ° C, preferably from 35 to 50 ° C, or from 2 to 20 ° C preferably 5 to 15 ° C.
    [0009]
    9. The method of claim 8, which comprises: - the application on the skin or integuments, preferably the nails, of a makeup composition according to any one of claims 5 and 6, or the subcutaneous injection a tattoo composition according to claim 7, and - the application to makeup or tattooing of at least one heat treatment cycle to at least a part of the make-up or tattoo, resulting in discoloration and recolouration or change color makeup or tattoo. ICG70047 Filing text 3037236 21
    [0010]
    10. Use of microcapsules comprising: (A) at least one electron donor leuco dye compound, (B) at least one electron acceptor compound, (C) a mixture comprising at least one compound of formula (I) 10 Wherein R1 represents a C5-C23 alkyl or alkenyl group, n represents an integer from 1 to 6, and at least one compound of formula (II) wherein R2 represents a C5-C23 alkyl or alkenyl group for the manufacture of a thermochromic composition for cosmetic or dermatological application or a tattoo application. 30
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    同族专利:
    公开号 | 公开日
    FR3037236B1|2017-05-26|
    WO2016198784A1|2016-12-15|
    引用文献:
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    JP5506224B2|2009-03-27|2014-05-28|三菱鉛筆株式会社|Thermal decolorizable ink composition|FR3063082B1|2017-02-17|2019-04-05|Societe Bic|NOVEL THERMOCHROME PIGMENT COMPOSITION COMPRISING A COMPOUND OF FORMULAAS A REACTIONAL MEDIUM|
    FR3065727B1|2017-04-27|2021-01-22|Soc Bic|NEW COMPOUNDS OF FORMULAAND THEIR USE IN THERMOCHROME PIGMENT COMPOSITIONS|
    FR3065728B1|2017-04-27|2020-11-20|Soc Bic|NEW COMPOUNDS OF FORMULAAND THEIR USE IN THERMOCHROME PIGMENT COMPOSITIONS|
    FR3065729B1|2017-04-27|2020-12-18|Soc Bic|NEW COMPOUNDS OF FORMULAAND THEIR USE IN THERMOCHROME PIGMENT COMPOSITIONS|
    GB201817196D0|2018-10-22|2018-12-05|Theunseen|Cosmetic composition|
    RU2730486C1|2019-10-09|2020-08-24|Общество с ограниченной ответственностью "ЮНИКОСМЕТИК"|Cosmetic procedures associated with keratin fibre heating|
    法律状态:
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    2016-12-16| PLSC| Search report ready|Effective date: 20161216 |
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    2021-03-03| PLFP| Fee payment|Year of fee payment: 7 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1555413A|FR3037236B1|2015-06-12|2015-06-12|MICROCAPSULES AND COMPOSITION FOR MAKE-UP OR THERMOCHROMIC TATTOO|FR1555413A| FR3037236B1|2015-06-12|2015-06-12|MICROCAPSULES AND COMPOSITION FOR MAKE-UP OR THERMOCHROMIC TATTOO|
    PCT/FR2016/051362| WO2016198784A1|2015-06-12|2016-06-07|Thermochromic makeup or tattooing microcapsules and composition|
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